US4421905A - Process for preparing polyimides end-capped with anhydride or isocyanate groups - Google Patents
Process for preparing polyimides end-capped with anhydride or isocyanate groups Download PDFInfo
- Publication number
- US4421905A US4421905A US06/420,567 US42056782A US4421905A US 4421905 A US4421905 A US 4421905A US 42056782 A US42056782 A US 42056782A US 4421905 A US4421905 A US 4421905A
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- United States
- Prior art keywords
- dianhydride
- polyimide
- acetylacetonate
- aromatic
- diisocyanato
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1003—Preparatory processes
- C08G73/1035—Preparatory processes from tetracarboxylic acids or derivatives and diisocyanates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
- C08G18/343—Polycarboxylic acids having at least three carboxylic acid groups
- C08G18/346—Polycarboxylic acids having at least three carboxylic acid groups having four carboxylic acid groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
Definitions
- This invention relates to the preparation of polyimides end-capped with anhydride or other groups. More specifically it relates to a process for the preparation of such polyimides by the reaction of aromatic dianhydrides with aromatic diisocyanates. Still more specifically it relates to such reaction conducted in the presence of a metal acetylacetonate such as aluminum acetylacetonate. Still more specifically this process allows the use of lower temperatures and avoids certain destructive effects such as the reduction of the anhydride activity and thereby makes them more effective in a reaction with epoxy compounds.
- the method including the solvent, used for preparing the polyimide dianhydride, is one that produces these intermediates with a high anhydride activity (I R ) and good conversion to imide structures.
- I R anhydride activity
- the high I R , good solubility and low fusion temperatures are desirable for good subsequent reaction with a polyepoxide.
- the Molar Ratio of starting monomers is represented as r m or X/Y, with X representing moles of diamine and Y the moles of dianhydride.
- Degree of Polymerization (DP)--Polyimides may be prepared by reacting X moles of diamine with Y moles of dianhydride. To produce an anhydride-terminated polyimide, Y is greater than X.
- the statistical average "degree of polymerization" (DP) may be calculated on the basis that the formation of the intermediate amic acid groups may be negated by the relatively long reaction periods used as compared to the relatively short time for amic acid formation. Therefore:
- n 1
- Degree of Imidization is equal to the amount of water distilled from the reaction divided by the amount of water theoretically to be removed by complete imidization. This is equal to (2n ⁇ 18) grams for making one gram mole of polyimide.
- Relative Reactivity is the ratio of the intensity peak ratio of the absorption peak of the anhydride group at 1840 cm -1 to that of the imide group at 1790 cm in the Infrared Spectrum of the polyimide.
- the number of equivalent weights of a component is the weight of the component divided by the equivalent weight of the component.
- polyimides may be prepared by the reaction of aromatic dianhydrides with aromatic diisocyanates in the presence of metal acetylacetonates, such as Al, Co, Ni, Fe and Zr, which compounds apparently allow the imidization or cyclization to be completed at lower temperatures so that anhydride activity will not be destroyed or reduced by reaction with amide groups that may be present in the solvent.
- metal acetylacetonates such as Al, Co, Ni, Fe and Zr
- the anhydride end-capped polyimide may be reacted with one mole of an aromatic diamine per terminal anhydride group to convert the "polyimide dianhydride" to the corresponding "polyimide diamine.”
- the product will be a "polyimide diisocyanate.”
- polyimide dianhydrides are represented by the formula: ##STR2## and the “polyimide diisocyanates” represented by the formula: ##STR3## in which formulas Ar' is a tetravalent aromatic organic radical, the four carbonyl groups being attached directly to separate carbon atoms and each pair of carbonyl groups being attached to adjacent carbon atoms in the Ar' radical except that in the case of the Ar' being a naphthalene radical, one or both pairs of the carbonyl groups may be attached to peri carbon atoms; Ar is a divalent aromatic radical; and n is an integer of at least one, preferably 1-20. It has been found that the polyimide dianhydride should have a high anhydride activity (I R ), namely at least 0.17 as measured by its infrared spectrum.
- I R anhydride activity
- polyimide dianhydrides in the presence of N-containing groups such as DMA, DMF, NMP, etc. which have the terminal anhydride groups intact so that the anhydride activity (I R ) is at least 0.17 and preferably higher.
- N-containing groups such as DMA, DMF, NMP, etc.
- Polyimides produced by the process of this invention may be represented generically by the formula: ##STR6## wherein Ar' and Ar are as defined above, and
- D is O ⁇ or OCN--Ar--N ⁇ ; and D' is ##STR7## or >CO.
- D represents O ⁇
- D' represents ##STR8##
- a polyimide dianhydride is represented.
- D represents >N--Ar--NCO
- D' represents OC ⁇
- Other combinations of the D and D' groups will represent a polyimide having one terminal isocyanate group and one anhydride group.
- polyimide dianhydrides may be more satisfactorily reacted with polyepoxide compounds, particularly with regard to the improved production of laminated products and coating compositions.
- any of the aromatic tetracarboxylic acid dianhydrides known in the prior art can be used.
- the useful dianhydrides are 3,3',4,4'-benzophenonetetracarboxylic acid dianhydride, pyromellitic dianhydride, 2,3,6,7-naphthalene tetracarboxylic acid dianhydride, 1,4,5,6-naphthalene-tetracarboxylic dianhydride, 3,3'4,4'-diphenyl tetracarboxylic acid dianhydride, 1,2,5,6-naphthalene tetracarboxylic acid dianhydride, 2,2'3,3'-diphenyl tetracarboxylic acid dianhydride, 2,2-bis(3,4-dicarboxyphenyl) propane dianhydride, 3,4,9,10-perylene t
- Diisocyanates useful in preparing the starting polyimides have the formula:
- Ar is a divalent aromatic organic radical.
- Preferred aromatic diisocyanates are those wherein Ar is a divalent benzenoid radical selected from the group consisting of: ##STR9## and multiples thereof connected to each other by R'", e.g.: ##STR10## wherein R'" is --CH ⁇ CH--, ##STR11## or an alkylene chain of 1-3 carbon atoms, wherein R V and R IV are each selected from the group consisting of alkyl and aryl radicals containing one to six carbon atoms, e.g., methyl, ethyl, hexyl, n-butyl, i-butyl and phenyl.
- aromatic diisocyanates which are suitable for use in the present invention are 1,4-phenylenediisocyanate, 1,3-phenylenediisocyanate, 2,4-tolylenediisocyanate, 2,5-tolylenediisocyanate, 2,6-tolyenediisocyanate, 3,5-tolyenediisocyanate, 4-chloro-1,3phenylenediisocyanate, 1-methoxy-2,4-phenylenediisocyanate, 1-methyl-3,5-diethyl-2,6-phenylenediisocyanate, 4,4'-diisocyanato-diphenyl propane, 4,4'-diisocyanato-diphenyl methane, 4,4'-diisocyanato-diphenyl sulfide, 3,3'-diisocyanato-diphenyl sulfone, 4,4'-diisocyanato-diphenyl sulf
- Preferred ddisocyanates are 4,4'-oxydiphenyldiisocyanates, 4,4'-sulfonyldiisocyanates, 4,4'-methylene diphneyldiisocyanates, 4,4'-diisocyanato-benzophenone, 4,4'-diisocyanato-stilbene and the phenylene diisocyanates.
- the polyimide forming reactions are conducted in a nitrogen-containing solvent.
- the specific solvent will depend on the particular aromatic polyimide used. In most cases the solvent is an aprotic organic compound having a dielectric constant between 35 and 45, preferably one which is water soluble.
- Representative aprotic compounds are N-N-dimethylformamide, N,N-diethylformamide, N,N-dimethylmethoxyacetamide, N-methyl caprolactam, caprolactam, N,N-dimethylacetamide, N,N-diethylacetamide, dimethyl sulfoxide, N-methlyl-alpha-pyrrolidone, tetramethylurea, hexamethylphosphoramide, N,N,N',N'-tetramethylethylmalonamide, N,N,N',N'-tetramethyl glutaramide, N,N,N',N'-tetramethylsuccinamide, thiobis(B,N-dimethylcarbamylmethyl) ether, N,N,N',N'-tetramethylfuraramide, methylsuccinonitrile, N,N-dimethylcyanocetamide, N,N-dimethyl-alpha-cyanopropionamide,
- Metal Acetylacetonates are available from the Harshaw Chemical Company. These have the formula: ##STR12## When the Me is Al, Co, Fe and Ni, "n" has a value of 3 and when Me is Zr, "n" has a value of 4.
- the acetylacetonate-promoted reaction is advantageously conducted at a temperature in the range of 70°-150° C., preferably in the range of 100°-140° C. When the temperature is in the upper portion of these ranges, the imidization reaction is substantially completed in 2-4 hours.
- the metal acetylacetonate is advantageously used in an amount of at least 0.005 gm, preferably at least 0.01 gm per equivalent weight of dianhydride and generally there is no need to exceed 1 gm of metal acetylacetonate to obtain the desired results.
- the metal acetylacetonate is used in an amount of 0.005-1 gm of metal acetylacetonate, preferably 0.01-0.05 gm per gm of aromatic dianhydride.
- NMP N-methyl-2-pyrrolidone
- a 2500 ml round bottom flask containing 1500 ml of NMP is heated to 150° C. and then a vacuum of about 29" (Hg) is applied to the system. The first 50 ml of the distillate is discarded.
- the collection of NMP distillate starts at 94° C./29" (Hg) and ends at T b -101/30" (HG).
- the total distillate collected is about 1300 ml, with about 150 ml of yellowish residual NMP discarded.
- the freshly distilled NMP is then run through the LINDE Molecular Sieve, Type 4A PLTS, sold by Union Carbide Corporation, Materials System Division.
- the DMF is also similarly distilled under vacuum and then dehydrated by Molecular Sieve as described above.
- the solution is cooled to about 60° C., then a solid powder mixture of 24.4 g of 2,4-toluenediamine (TDA) (0.2 moles) and 96.67 g of 3,3',4,4'-benzophenonetetracarboxylic dianhydride (BTDA) (0.3 mole) is added into the solution slowly in order to control the exotherm reaction and solution temperature.
- TDA 2,4-toluenediamine
- BTDA 3,3',4,4'-benzophenonetetracarboxylic dianhydride
- DABCO 1,4-diazabicyclo-(2,2,2) octane
- the degree of imidization at 145° C. is about 53%, at 153° C. about 84%, at 157° C. about 93%. After 2 hours above 157° C. to the maximum of 160° C., the imidization is completed. A total of 7.2 g of distilled H.sub. 2 O is recovered. The total reaction time above 150° C. is about 4 hours. The polyimide is precipitated by adding 700 ml of acetone. The yield is 108 g or about 95%. The r m for this product is 0.667; the DP is 5; n is 2 and the C is 1.0.
- This polyimide is designated as: [BTDA-DTA] 2 [AH] 2 which is soluble in both NMP and DMF. This procedure is used with phenol, m-cresol, dimethylformamide (DMF) and N-methyl-alpha-pyrrolidone (NMP) respectively.
- the relative reactivities (I R ) of the respective polyimide dianhydrides are measured as the ratio of the Infrared Spectrum adsorption peak of the anhydride at 1840 cm -1 to that of the imide at 1790 cm -1 .
- the reactivities are reported below in TABLE I.
- the polyimide dianhydrides A, B and C prepared in Example I are tested for reactivity with a Novolac epoxy resin, marketed by Ciba-Geigy, EPN 1138 which has an epoxy equivalent of 185-195.
- EPN 1138 which has an epoxy equivalent of 185-195.
- 25 g of EPN 1138 (0.1351 equivalent) is mixed with 70 g of the polyimide dianhydride A, B or C and 168 g of NMP to solutions of 36% and heated at the temperatures and for the periods indicated below in TABLE II.
- the ratio (R) of epoxy equivalents to anhydride equivalents in each case is 1.10.
- the respective viscosities are also reported in TABLE II.
- the respective viscosities relate to the respective anhydride activities as reported in Example I.
- the above polyimide-epoxy resin solutions are applied individually onto 181E type glass cloth by hand, spreading and rolling it by using a roller over both faces of the glass cloth.
- the impregnated fabrics are dried in a well ventilated hood for at least 48 hours, then in a forced air oven at 65° C.-75° C. for about one hour and cut into strips of 1/2" ⁇ 5".
- About 25 of the strips are loaded into a mold at temperatures of about 167° C. After the press is closed and pressure is applied at about 200 psi, the temperature of the mold is increased and held at 180° C. for 8 minutes. The die is then opened and the specimen is removed for testing. The tested results are listed below in Table IIa.
- a polyimide-epoxy product, using an oligo-imide dianhydride [BTDA-TDA] 5 [AH] 2 prepared from NMP solution (I R 0.12, C--1.0), laminated according to the above procedure as for the above preparation also delaminates upon molding.
- a 200 ml round bottom flask is loaded with 86 ml of N-methyl-alpha-pyrrolidone (NMP), 16.1 gm (0.1 equivalent) of 3,4,3',4'-benzophenonetetracarboxylic dianhydride (BTDA), 6.5 gm (0.075 equivalent) of toluene diisocyanate* and 0.3 gm aluminum acetylacetonate.
- NMP N-methyl-alpha-pyrrolidone
- BTDA 3,4,3',4'-benzophenonetetracarboxylic dianhydride
- BTDA 3,4,3',4'-benzophenonetetracarboxylic dianhydride
- BTDA 3,4,3',4'-benzophenonetetracarboxylic dianhydride
- BTDA 3,4,3',4'-benzophenonetetracarboxylic dianhydride
- BTDA 3,4,3',4'-benzophen
- a polyimide dianhydride prepared as in Example III is added (70 gm) and is mixed with 25 g of EPN 1138 (0.1351 equivalent) and 170 gm of NMP to give a 36% solution and heated 80° C. for 5 hours.
- the laminates are prepared by hand spreading the above reaction product and then using a roller over both faces of the glass cloth.
- the impregnated fabrics are dried in a well ventilated hood for at least 48 hours, then in a forced air oven at 65° C.-75° C. for about one hour.
- About 25 of the strips are loaded into a mold at temperatures of about 167° C. After the press is closed and pressure is applied at about 200 psi, the temperature of the mold is increased to about 180° C. for about 8 minutes.
- the die is then opened and the specimen is removed for testing.
- the tested laminate has a flexural strength of 51.0 ( ⁇ 10.sup. 3) psi and a modulus of 3.1 ( ⁇ 10 6 )
- a polyimide diamine is prepared by repeating the procedure of Example III except that a Dean-Stark trap is used, an aromatic diamine is used instead of the diisocyanate and toluene is used to separate water from the reaction.
- the charge comprises 87 ml of NMP, 10 ml of toluene, 24.17 gm (0.15 equivalent) of BTDA, 12.2 gm (0.2 equivalent) of 2,4-toluenediamine, and 0.3 gm of Al acetylacetonate.
- the anhydride/amine ratio is 0.75/1.
- the Al acetylacetonate is used in this case to reduce or avoid decomposition byproducts in the subsequent molding.
- the mixture is heated first at 60° C. for 2 hours and then at 160° C. for 2 hours during which time 2.7 gms of water is collected.
- the product has a n value of 3 and has the formula:
- Example II The entire dianhydride product of Example II is well mixed with 27.75 gm (0.15 equivalent) of EPN 1138 and allowed to stand at room temperature for one hour. Then the polyimide diamine prepared in Example V is added and mixed before heating at 60° C. for 20 minutes to give a viscosity of 400 cps. This product is dried at room temperature for 48 hours and then used to laminate glass cloth E 180 (Clark-Schweibel fiberglass) as above. The laminates are compressed at 200 psi and heated at 160°-180° C. for 10 minutes. The laminated product has a flexural strength of 73.6 ⁇ 10 3 psi and modulus of 5.0 ⁇ 10 6 psi.
- Example III The procedure of Example III is repeated a number of times with similar high I R values as obtained in Example III using in place of the Al acetylacetonate equivalent amounts respectively of:
- Example III The procedure of Example III is repeated a number of times to give polyimide dianhydrides of similar I R values as obtained in Example III, using in place of the BTDA equivalent weights respectively of:
- polyimide dianhydrides of Examples III, VII and X when reacted with EPN 1138 polyepoxide are used satisfactorily to give laminated products in accordance with the procedure of Example II and particularly when a polyimide diamine is also added as in Example VI.
Abstract
Description
DP=(1+r.sub.m)/(1-r.sub.m)
(DP-1)/2=r.sub.m /(1-r.sub.m)
OCN--Ar--NCO
TABLE I ______________________________________ Polyimide Dianhydride Solvent I.sub.R ______________________________________ A NMP 0.16 B DMF 0 C Phenol 0.33 D m-cresol 0.36 ______________________________________
TABLE II ______________________________________ Resultant Polyimide Solvent Used Viscosity Dianhydride In Prep. Temp. Time Centipoises ______________________________________ A NMP 90° C. 7 hrs. 32 B DMF 80° C. 8 hrs. 20 C.sub.1 Phenol 65° C. 4 hrs. 260 C.sub.2 Phenol 80° C. 4 hrs. 1,150 ______________________________________
TABLE IIa ______________________________________ Properties of Polyimide Dianhydride-Epoxy Laminate Flexural Strength Modulus (× 10.sup.-3 psi) (× 10.sup.-6 psi) Resin Content ______________________________________ A Delamination after opening of press -- B Delamination after opening of press -- C.sub.1 48.6 3.1 26.3 ± 2.5% C.sub.2 57.5 3.6 27.3 ± 2.2% ______________________________________
O[(OC).sub.2 C.sub.6 H.sub.4 C(O)C.sub.6 H.sub.4 (CO).sub.2 N--Ar--N].sub.3 (CO).sub.2 Ar'(CO).sub.2 O
H.sub.2 [N--Ar--N(CO).sub.2 Ar'(CO).sub.2 ].sub.3 NArNH.sub.2
Claims (13)
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US06/420,567 US4421905A (en) | 1982-09-20 | 1982-09-20 | Process for preparing polyimides end-capped with anhydride or isocyanate groups |
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US06/420,567 US4421905A (en) | 1982-09-20 | 1982-09-20 | Process for preparing polyimides end-capped with anhydride or isocyanate groups |
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4861806A (en) * | 1986-09-19 | 1989-08-29 | Ciba-Geigy Corporation | Process for curing polyisocyanate coatings in the presence of a ferrocenium compound |
EP1829910A1 (en) * | 2004-12-24 | 2007-09-05 | Mitsubishi Gas Chemical Company, Inc. | Low water-absorptive polyimide resin and method for producing same |
KR101292546B1 (en) * | 2009-07-16 | 2013-08-12 | 주식회사 엘지화학 | Polyimide type hardner and photosensitive resin composition including the hardner |
US20190083921A1 (en) * | 2017-09-21 | 2019-03-21 | Kabushiki Kaisha Toshiba | Carbon dioxide absorbent and apparatus of separating and recovering carbon dioxide |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3682860A (en) * | 1969-03-03 | 1972-08-08 | Toray Industries | Thermally stable polymers and method of their production |
US3997513A (en) * | 1972-04-04 | 1976-12-14 | Nitto Electric Industrial Co., Ltd. | Solution for forming thermal resisting polymers |
US4094864A (en) * | 1974-11-07 | 1978-06-13 | The Upjohn Company | Preparation of polyamideimide from diisocyanate with alkali metal lactamate catalyst |
-
1982
- 1982-09-20 US US06/420,567 patent/US4421905A/en not_active Expired - Fee Related
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3682860A (en) * | 1969-03-03 | 1972-08-08 | Toray Industries | Thermally stable polymers and method of their production |
US3997513A (en) * | 1972-04-04 | 1976-12-14 | Nitto Electric Industrial Co., Ltd. | Solution for forming thermal resisting polymers |
US4094864A (en) * | 1974-11-07 | 1978-06-13 | The Upjohn Company | Preparation of polyamideimide from diisocyanate with alkali metal lactamate catalyst |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4861806A (en) * | 1986-09-19 | 1989-08-29 | Ciba-Geigy Corporation | Process for curing polyisocyanate coatings in the presence of a ferrocenium compound |
EP1829910A1 (en) * | 2004-12-24 | 2007-09-05 | Mitsubishi Gas Chemical Company, Inc. | Low water-absorptive polyimide resin and method for producing same |
US20080132667A1 (en) * | 2004-12-24 | 2008-06-05 | Takashi Makinoshima | Low Water-Absorptive Polyimide Resin and Method for Producing Same |
EP1829910A4 (en) * | 2004-12-24 | 2008-09-17 | Mitsubishi Gas Chemical Co | Low water-absorptive polyimide resin and method for producing same |
US7659360B2 (en) | 2004-12-24 | 2010-02-09 | Mitsubishi Gas Chemical Company, Inc. | Low water-absorptive polyimide resin and method for producing same |
KR101292546B1 (en) * | 2009-07-16 | 2013-08-12 | 주식회사 엘지화학 | Polyimide type hardner and photosensitive resin composition including the hardner |
US20190083921A1 (en) * | 2017-09-21 | 2019-03-21 | Kabushiki Kaisha Toshiba | Carbon dioxide absorbent and apparatus of separating and recovering carbon dioxide |
US11123683B2 (en) * | 2017-09-21 | 2021-09-21 | Kabushiki Kaisha Toshiba | Carbon dioxide absorbent and apparatus of separating and recovering carbon dioxide |
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